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WO2013042503A1 - Batterie secondaire non aqueuse - Google Patents

Batterie secondaire non aqueuse Download PDF

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Publication number
WO2013042503A1
WO2013042503A1 PCT/JP2012/071168 JP2012071168W WO2013042503A1 WO 2013042503 A1 WO2013042503 A1 WO 2013042503A1 JP 2012071168 W JP2012071168 W JP 2012071168W WO 2013042503 A1 WO2013042503 A1 WO 2013042503A1
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Prior art keywords
fluorine
secondary battery
formula
represented
volume
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English (en)
Japanese (ja)
Inventor
彰信 中村
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NEC Corp
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NEC Corp
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Priority to US14/345,900 priority Critical patent/US20140227611A1/en
Priority to JP2013534643A priority patent/JP6036697B2/ja
Publication of WO2013042503A1 publication Critical patent/WO2013042503A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0034—Fluorinated solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/004—Three solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a non-aqueous secondary battery.
  • lithium-ion batteries can be used as power sources for small devices such as mobile phones and laptop computers, as well as power sources for motorcycles and automobiles, and primary batteries such as solar cells and wind power generation. Development for application is actively underway.
  • carbonate-based non-aqueous solvents are used for the electrolyte of lithium ion batteries. This is because the carbonate-based solvent is excellent in electrochemical resistance and is inexpensive in cost.
  • mixed electrolytes of chain carbonates such as diethyl carbonate (DEC) and dimethyl carbonate (DMC) are used together with cyclic carbonates such as ethylene carbonate (EC) and propylene carbonate (PC). Since cyclic carbonate has a high dielectric constant, it has a function of dissolving / dissociating lithium salts such as LiPF 6 , and chain carbonate has a function of improving the diffusibility of lithium ions in the electrolytic solution because of its low viscosity.
  • Patent Documents 1 to 3 discuss a technique for improving oxidation resistance under a high voltage by using a fluorine compound as a solvent for the electrolytic solution.
  • Patent Document 4 discloses a nonaqueous electrolytic solution containing a high concentration of fluorine-substituted carboxylic acid ester.
  • Patent Document 5 discloses a method of using 4-fluoroethylene carbonate (FEC) as a film forming agent on the negative electrode together with a chain-like fluorine-substituted carboxylic acid ester.
  • FEC 4-fluoroethylene carbonate
  • Patent Documents 1 to 3 are all techniques using a chain-like fluorine-substituted carboxylic acid ester.
  • the fluorine-substituted carboxylic acid ester has a low dielectric constant and cannot be used alone to dissolve a lithium salt such as LiPF 6 , the combined use of a carbonate-based solvent is essential.
  • a lithium ion battery using a high-voltage positive electrode such as a 5 V class positive electrode, decomposition of the carbonate-based solvent component has progressed, and a sufficient effect may not be obtained.
  • an object of the present embodiment is to provide a non-aqueous secondary battery in which decomposition of the electrolytic solution is effectively suppressed even under high voltage and high temperature conditions and excellent in long-term cycle characteristics.
  • a non-aqueous secondary battery comprising an electrolytic solution containing a supporting salt and a non-aqueous electrolytic solvent
  • the nonaqueous electrolytic solvent includes a sulfone compound represented by the following formula (1) and a fluorine-containing ester compound represented by the following formula (A):
  • the content of the sulfone compound is 20% by volume or more and 70% by volume or less in the nonaqueous electrolytic solvent
  • the content of the fluorine-containing ester compound is 20% by volume or more and 60% by volume or less in the non-aqueous electrolytic solvent.
  • R 1 and R 2 each independently represents a substituted or unsubstituted alkyl group.
  • the carbon atom of R 1 and the carbon atom of R 2 are bonded via a single bond or a double bond. And may form a ring structure).
  • R a and R b each independently represents an alkyl group or a fluorine-substituted alkyl group, and at least one of R a and R b is a fluorine-substituted alkyl group.
  • the present embodiment it is possible to provide a non-aqueous secondary battery that suppresses the decomposition of the electrolytic solution under high voltage and high temperature conditions and has excellent long-term cycle characteristics.
  • FIG. 3 is a schematic cross-sectional view showing a structure of an electrode element included in a laminated laminate type secondary battery.
  • the mechanism of the effect of this embodiment is estimated as follows. First, the fluorine-containing ester compound having excellent oxidation resistance has an adsorption action on the electrode of the lithium ion battery, whereby a stable film is formed on the electrode surface. And since decomposition
  • the lithium salt can be sufficiently dissolved / dissociated by the action of the sulfone compound having compatibility with the fluorine-containing ester compound, and a practical level of lithium ion conductivity can be obtained.
  • the sulfone compound has a relatively excellent oxidation resistance and is a film formed by a fluorine-containing ester compound. Thus, it is presumed that reductive decomposition is effectively and synergistically suppressed. These inferences do not limit the present invention.
  • the non-aqueous secondary battery in the present embodiment includes an electrolytic solution obtained by dissolving a supporting salt in a non-aqueous electrolytic solvent.
  • the nonaqueous electrolytic solvent in the present embodiment includes at least a sulfone compound represented by the following formula (1) and a fluorine-containing ester compound represented by the following formula (A) as a solvent. Moreover, content of the said sulfone compound is 20 volume% or more and 70 volume% or less in a nonaqueous electrolytic solvent, and content of the said fluorine-containing ester compound is 20 volume% or more and 60 volume% or less in a nonaqueous electrolytic solvent.
  • the nonaqueous electrolytic solvent in this embodiment includes a sulfone compound represented by the following formula (1) as a solvent.
  • R 1 and R 2 each independently represents a substituted or unsubstituted alkyl group.
  • the carbon atom of R 1 and the carbon atom of R 2 are bonded via a single bond or a double bond. And may form a ring structure).
  • the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and preferably 1 to 4 carbon atoms. Particularly preferred.
  • the alkyl group includes linear, branched, or cyclic groups, and is preferably linear or branched.
  • examples of the substituent include, for example, an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group),
  • An aryl group for example, a phenyl group, a naphthyl group
  • a halogen atom for example, a chlorine atom, a bromine atom, a fluorine atom
  • the carbon atom of R 1 and the carbon atom of R 2 are preferably bonded through a single bond to form a cyclic structure.
  • the sulfone compound is preferably a cyclic sulfone compound represented by the following formula (2).
  • R 3 represents a substituted or unsubstituted alkylene group
  • the alkylene group preferably has 4 to 16 carbon atoms, more preferably 4 to 14 carbon atoms, still more preferably 4 to 12 carbon atoms, and particularly preferably 4 to 10 carbon atoms.
  • examples of the substituent include an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group), halogen atom (for example, chlorine atom, bromine atom, fluorine atom). Atom) and the like.
  • the cyclic sulfone compound is more preferably a compound represented by the following formula (3).
  • n is an integer from 1 to 10.
  • m is preferably an integer of 1 to 8, more preferably an integer of 1 to 6, and an integer of 1 to 4. More preferably, it is an integer of any one of 1 to 3.
  • Preferred examples of the cyclic sulfone compound represented by the formula (3) include tetramethylene sulfone, pentamethylene sulfone, hexamethylene sulfone and the like. Since these materials are compatible with the fluorine-containing ester compound and have a relatively high dielectric constant, they have the advantage of being excellent in the dissolution / dissociation action of the lithium salt.
  • cyclic sulfone compound having a substituent examples include 3-methylsulfolane and 2,4-dimethylsulfolane. Since these materials are compatible with the fluorine-containing ester compound and have a relatively high dielectric constant, they have the advantage of being excellent in the dissolution / dissociation action of the lithium salt.
  • the sulfone compound may be a chain sulfone compound, and examples of the chain sulfone compound include ethyl methyl sulfone, ethyl isopropyl sulfone, ethyl isobutyl sulfone, dimethyl sulfone, and diethyl sulfone.
  • ethyl methyl sulfone, ethyl isopropyl sulfone, and ethyl isobutyl sulfone are preferable. Since these materials are compatible with the fluorine-containing ester compound and have a relatively high dielectric constant, they have the advantage of being excellent in the dissolution / dissociation action of the lithium salt.
  • the sulfone compounds can be used alone or in combination of two or more.
  • the nonaqueous electrolytic solvent in the present embodiment can contain at least one sulfone compound selected from the compounds represented by formula (1).
  • the content of the sulfone compound is 20% by volume or more and 70% by volume or less in the nonaqueous electrolytic solvent.
  • the lithium salt can be sufficiently dissolved by the action of the sulfone compound having compatibility with the fluorine-containing ester compound, and a practical level of lithium ion conductivity is obtained. It is done.
  • the excessive increase in the viscosity of electrolyte solution can be suppressed by making content of a sulfone compound 70 volume% or less.
  • the content of the sulfone compound is preferably 23% by volume or more and 60% by volume or less, and more preferably 25% by volume or more and 50% by volume or less in the nonaqueous electrolytic solvent.
  • the nonaqueous electrolytic solvent in the present embodiment includes a fluorine-containing ester compound represented by the following formula (A) as a solvent.
  • Fluorine-substituted ester compounds have the advantages of excellent oxidation resistance and relatively low viscosity. For this reason, it is possible to prevent oxidative decomposition under high voltage and to have little influence on the lithium ion conductivity and the electrolytic solution characteristics.
  • R a and R b each independently represents an alkyl group or a fluorine-substituted alkyl group, and at least one of R a and R b is a fluorine-substituted alkyl group.
  • the alkyl group or the fluorine-substituted alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and 1 to 6 carbon atoms. Is more preferable, and 1 to 4 is particularly preferable.
  • the fluorine-substituted alkyl group represents a substituted alkyl group having a structure in which at least one hydrogen atom of the unsubstituted alkyl group is substituted with a fluorine atom.
  • the alkyl group includes a linear, branched or cyclic group, but the fluorine-substituted alkyl group is preferably linear.
  • R a and R b are each independently a fluorine-substituted alkyl group.
  • R a is an alkyl group and R b is a fluorine-substituted alkyl group.
  • R a is a fluorine-substituted alkyl group and R b is an alkyl group.
  • R a and R b represents an alkyl group, and the other represents a fluorine-substituted alkyl group.
  • the fluorine-containing ester compound having such a structure has excellent oxidation resistance and good compatibility with other solvents.
  • R a represents a fluorine-substituted alkyl group and R b represents an alkyl group.
  • the fluorine-containing ester compound is a compound represented by the following Formula (B) It is more preferable that
  • R 1 is represented by —C n H 2n + 1-m F m , n is an integer of 1 to 3, and m is an integer of 1 to 2n + 1)
  • R 2 is represented by —C 1 H 2l + 1 , and 1 represents an integer of 1 to 3.
  • fluorine-containing ester compound is more preferably a compound represented by the following formula (C) or (D).
  • R 5 is —CH 3 , —C 2 H 5 , or —C 3 H 7 ).
  • R 8 is —CH 3 , —C 2 H 5 , or —C 3 H 7 ).
  • fluorine-containing ester compound methyl 2,2,3,3-tetrafluoropropionate or ethyl 2,2,3,3-tetrafluoropropionate is preferable.
  • These compounds have the advantage of good practical properties such as viscosity, boiling point, melting point, flash point, etc. in addition to good oxidation resistance.
  • Table 1 shows compounds that can be preferably used as the fluorine-containing ester compound.
  • Fluorine-containing ester compounds can be used alone or in combination of two or more.
  • the nonaqueous electrolytic solvent in the present embodiment can contain at least one fluorine-containing ester compound selected from the compounds represented by formula (A).
  • Content of a fluorine-containing ester compound is 20 volume% or more and 60 volume% or less in a non-aqueous electrolytic solvent.
  • the content of the fluorine-containing ester compound is 20% by volume or more, a film can be effectively formed on the negative electrode surface, and decomposition of the electrolytic solution can be more effectively suppressed.
  • the content of the fluorine-containing ester compound is 60% by volume or less, it is possible to sufficiently ensure the solubility / dissociation property of a thium salt such as LiPF 6 and the compatibility with other solvents. From these viewpoints, the content of the fluorine-containing ester compound is preferably 25% by volume or more and 55% by volume or less in the nonaqueous electrolytic solvent, and more preferably 30% by volume or more and 50% by volume or less.
  • the nonaqueous electrolytic solvent can contain propylene carbonate (PC).
  • PC propylene carbonate
  • the content of propylene carbonate in the nonaqueous electrolytic solvent is preferably 10% to 50% by volume, more preferably 15% to 40% by volume, and 20% to 30% by volume. More preferably it is.
  • the non-aqueous electrolytic solvent may contain other solvent components, and as other solvent components, for example, carbonates, chlorinated hydrocarbons, ethers, ketones, nitriles and the like are preferably used.
  • solvent components more specifically, for example, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), ⁇ -butyrolactone (GBL), diethyl carbonate (DEC), dimethyl carbonate (DMC) ), Ethyl methyl carbonate (EMC), and the like.
  • EC ethylene carbonate
  • PC propylene carbonate
  • BC butylene carbonate
  • GBL ⁇ -butyrolactone
  • DEC diethyl carbonate
  • DMC dimethyl carbonate
  • EMC Ethyl methyl carbonate
  • what substituted a part of functional group of these solvents with fluorine can also be used.
  • the nonaqueous electrolytic solvent of this embodiment can contain a chain fluorine-containing ether compound represented by the following formula (I).
  • chain fluorine-containing ether compounds are used in combination with fluorine-containing ester compounds, in addition to good oxidation resistance, they have relatively high resistance to chemical reactivity with acids, alkalis, moisture, etc. The stability of the electrolyte is improved over a wider range of conditions.
  • R a and R b each independently represents an alkyl group or a fluorine-substituted alkyl group, and at least one of R a and R b is a fluorine-substituted alkyl group.
  • the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8, more preferably 1 to 6, and more preferably 1 to 4. Particularly preferred. Further, in the formula (I), the alkyl group includes a linear, branched or cyclic group, but is preferably a linear group.
  • At least one of R a and R b is a fluorine-substituted alkyl group.
  • the fluorine-substituted alkyl group represents a substituted alkyl group having a structure in which at least one hydrogen atom of the unsubstituted alkyl group is substituted with a fluorine atom.
  • the fluorine-substituted alkyl group is preferably linear.
  • R a and R b are each independently preferably a fluorine-substituted alkyl group having 1 to 6 carbon atoms, and more preferably a fluorine-substituted alkyl group having 1 to 4 carbon atoms.
  • the chain fluorine-containing ether compound is preferably a compound represented by the following formula (II) from the viewpoint of voltage resistance and compatibility with other solvents.
  • n 1 to 8
  • Y 1 to Y 8 are each independently a fluorine atom or a hydrogen atom, provided that at least one of Y 1 to Y 3 is a fluorine atom.
  • At least one of Y 4 to Y 8 is a fluorine atom).
  • Y 2 and Y 3 may be independent for each n.
  • chain fluorine-containing ether compound is more preferably represented by the following formula (III) from the viewpoint of the viscosity of the electrolytic solution and compatibility with other solvents.
  • n is 1, 2, 3 or 4.
  • X 1 to X 8 are each independently a fluorine atom or a hydrogen atom. However, at least one of X 1 to X 4 is a fluorine atom, and at least one of X 5 to X 8 is a fluorine atom. X 1 to X 4 may be independent for each n.
  • n is preferably 1 or 2, and n is more preferably 1.
  • the atomic ratio of fluorine atoms to hydrogen atoms is preferably 1 or more.
  • chain fluorine-containing ether compounds examples include CF 3 OCH 3 , CF 3 OC 2 H 6 , F (CF 2 ) 2 OCH 3 , F (CF 2 ) 2 OC 2 H 5 , and F (CF 2 ) 3 OCH.
  • the content of the chain fluorine-containing ether compound in the electrolytic solution is, for example, 5 to 30% by mass.
  • the content of the chain fluorine-containing ether compound in the electrolytic solution is preferably 5 to 25% by mass, more preferably 7 to 20% by mass, and further preferably 10 to 15% by mass. preferable.
  • the content of the chain fluorine-containing ether compound in the nonaqueous electrolytic solvent is, for example, 5% by volume or more and 30% by volume or less.
  • the content of the chain fluorine-containing ether compound in the nonaqueous electrolytic solvent is preferably 5% by volume or more and 25% by volume or less, more preferably 7% by volume or more and 20% by volume or less. More preferably, the content is from 15% to 15% by volume.
  • An example of the supporting salt used in the present embodiment is a lithium salt.
  • the lithium salt include LiPF 6 , LiAsF 6 , LiAlCl 4 , LiClO 4 , LiBF 4 , LiSbF 6 , LiCF 3 SO 3 , LiC 4 F 9 CO 3 , LiC (CF 3 SO 2 ) 2 , LiN (CF 3 SO 2) 2, LiN (C 2 F 5 SO 2) 2, LiB 10 Cl 10, lower aliphatic carboxylic acid lithium carboxylate, chloroborane lithium, lithium tetraphenylborate, LiCl, LiBr, LiI, LiSCN, LiCl, Li Examples include imide salts.
  • the concentration of the lithium salt in the electrolytic solution is, for example, 0.5 mol / l to 1.5 mol / l. By setting it as this range, it can be set as the electrolyte solution which has moderate density, a viscosity, and electrical conductivity.
  • the electrolyte solution composition and the lithium salt concentration may be appropriately selected and adjusted in consideration of the environment in which the battery is used, optimization for battery applications, and the like.
  • the electrolytic solution is not limited to a liquid one but may be a gel.
  • the electrolytic solution is contained in a polymer electrolyte, and the polymer electrolyte is disposed in the secondary battery in a state where the polymer is swollen by the electrolytic solution.
  • the polymer electrolyte is excellent in terms of liquid leakage and gas generation suppression.
  • additives can be contained in the electrolytic solution.
  • the additive include aliphatic carboxylic acid esters such as methyl formate, methyl acetate and ethyl propionate, ⁇ -lactones such as ⁇ -butyrolactone, 1,2-ethoxyethane (DEE), ethoxymethoxyethane (EME).
  • cyclic ethers such as tetrahydrofuran and 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, acetamide, dimethylformamide, dioxolane, acetonitrile, propylnitrile, nitromethane, ethyl monoglyme, phosphorus Acid triester, trimethoxymethane, dioxolane derivative, sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, propylene carbonate derivative, tetra Hydrofuran derivatives, ethyl ether, 1,3-propane sultone, anisole, N-methylpyrrolidone and the like can be mentioned.
  • cyclic ethers such as tetrahydrofuran and 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-di
  • the amount of the non-aqueous electrolytic solvent is not particularly limited, and can be appropriately selected within a range where the effects of the present embodiment can be achieved.
  • the amount of the nonaqueous electrolytic solvent with respect to 100 parts by mass of the electrolytic solution is, for example, 80 parts by mass or more, preferably 85 parts by mass or more, more preferably 90 parts by mass or more, and 95 parts by mass or more. More preferably, it is particularly preferably 98 parts by mass or more.
  • the positive electrode active material is not particularly limited as long as lithium ions can be inserted during charge and desorbed during discharge.
  • a known material can be used.
  • the effect of this embodiment can be obtained more effectively by selecting the lithium manganese composite oxide as the positive electrode active material.
  • Lithium manganese composite oxide is known to cause elution of manganese components due to reaction with the electrolytic solution and deteriorate battery characteristics, but in this embodiment, unnecessary reaction between the positive electrode and the electrolytic solution can be suppressed. Therefore, the effect can be obtained more remarkably.
  • the lithium transition metal oxide is not particularly limited.
  • lithium manganate having a layered structure such as LiMnO 2 , Li x Mn 2 O 4 (0 ⁇ x ⁇ 2) or manganese having a spinel structure is used.
  • Examples thereof include lithium transition metal oxides; those having an olivine structure such as LiFePO 4 ; those lithium transition metal oxides in which Li is more excessive than the stoichiometric composition.
  • These materials can be used individually by 1 type or in combination of 2 or more types.
  • lithium manganese composite oxide for example, a so-called 4V class manganese spinel represented by the following formula can be used.
  • lithium manganese composite oxide those capable of occluding and releasing lithium at a metal lithium counter electrode potential of 4.5 V or more are preferable, and a lithium-containing composite oxide having a plateau at a metal lithium counter electrode potential of 4.5 V or more It is more preferable to use
  • lithium-containing composite oxides include spinel-type lithium manganese composite oxides, olivine-type lithium manganese-containing composite oxides, and reverse spinel-type lithium manganese-containing composite oxides.
  • M represents Ni, Co, Fe
  • spinel type lithium manganese composite oxide is preferable from the viewpoint of safety.
  • lithium manganese composite oxide having a plateau at 4.5 V or higher
  • M is at least selected from Ni, Co, Fe, Cr and Cu. It is one kind of metal and contains at least Ni.
  • A is at least one kind of metal selected from Si, Ti, Mg, and Al.
  • lithium manganese composite oxides it is particularly preferable to use 5V class manganese spinel.
  • 5V class manganese spinel the effect of this embodiment can be exhibited more by the decomposition inhibitory effect of the electrolyte solution under a high voltage.
  • the binder for the positive electrode is not particularly limited.
  • polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer Rubber, polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamideimide and the like can be used.
  • polyvinylidene fluoride is preferable from the viewpoint of versatility and low cost.
  • the amount of the positive electrode binder used is preferably 2 to 10 parts by mass with respect to 100 parts by mass of the positive electrode active material from the viewpoints of “sufficient binding force” and “higher energy” which are in a trade-off relationship. .
  • nickel, copper, silver, aluminum, and alloys thereof are preferable in view of electrochemical stability.
  • the shape include foil, flat plate, and mesh. In particular, copper foil and aluminum foil are preferable.
  • a conductive auxiliary material may be added to the positive electrode active material layer containing the positive electrode active material for the purpose of reducing impedance.
  • the conductive auxiliary material include carbonaceous fine particles such as graphite, carbon black, and acetylene black.
  • the positive electrode can be produced, for example, by preparing a positive electrode slurry by mixing lithium manganese composite oxide, a conductive agent and a positive electrode binder, and forming the positive electrode slurry on a positive electrode current collector.
  • a carbon material a metal substance such as Al, a conductive oxide powder, or the like can be used.
  • a binder a resin binder such as polyvinylidene fluoride can be used.
  • a metal thin film mainly composed of Al or the like can be used.
  • Negative Electrode The negative electrode active material in the present embodiment is not particularly limited as long as lithium ions can be inserted during charge and desorbed during discharge.
  • a known material can be used.
  • the negative electrode active material include carbon materials such as graphite, coke, and hard carbon, lithium alloys such as lithium-aluminum alloy, lithium-lead alloy, and lithium-tin alloy, lithium metal, Si, SnO 2 , and SnO. , TiO 2 , Nb 2 O 3 , SiO, and the like are metal oxides whose base potential is lower than that of the lithium manganese composite oxide. Of these materials, the effect of the present embodiment is further exhibited by using graphite. When graphite is used for the negative electrode, due to its potential characteristics and surface chemical characteristics, it is often more reactive with non-aqueous electrolytes than other materials, and the electrolyte tends to decompose. In the present embodiment, an unnecessary reaction between the negative electrode and the electrolytic solution can be prevented, so that the effect of the present embodiment is further exhibited.
  • carbon materials such as graphite, coke, and hard carbon
  • lithium alloys such as lithium-aluminum alloy, lithium-lead alloy, and lithium-t
  • the negative electrode can be produced, for example, by forming a negative electrode active material layer containing a negative electrode active material and a negative electrode binder on a negative electrode current collector.
  • Examples of the method for forming the negative electrode active material layer include a doctor blade method, a die coater method, a CVD method, and a sputtering method.
  • a thin film of aluminum, nickel, or an alloy thereof may be formed by a method such as vapor deposition or sputtering to form a negative electrode current collector.
  • the negative electrode active material layer may contain a conductive aid such as carbon from the viewpoint of improving conductivity.
  • the binder for the negative electrode is not particularly limited.
  • polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer Rubber, polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamideimide and the like can be used.
  • polyimide or polyamideimide is preferable because of its high binding properties.
  • the amount of the binder for the negative electrode to be used is preferably 7 to 20 parts by mass with respect to 100 parts by mass of the negative electrode active material from the viewpoints of “sufficient binding force” and “high energy” which are in a trade-off relationship. .
  • nickel, copper, silver, aluminum, and alloys thereof are preferable in view of electrochemical stability.
  • Examples of the shape include foil, flat plate, and mesh. In particular, copper foil is preferable.
  • the separator is not particularly limited, and for example, a polyolefin microporous film such as polyethylene or polypropylene, or a cellulose film can be used.
  • Exterior Body can be appropriately selected as long as it is stable to the electrolytic solution and has a sufficient water vapor barrier property.
  • Examples of the shape of the exterior body include a cylindrical shape, a square shape (can shape), and a flat plate shape.
  • the outer package is preferably a flat plate using a laminate film.
  • a flat secondary battery using a laminate film for the outer package is excellent in heat dissipation. Therefore, it is excellent in providing a large-capacity secondary battery that inputs and outputs large energy.
  • a laminate-type secondary battery an aluminum laminate film, a SUS laminate film, a silica-coated polypropylene film, a polyethylene laminate film, or the like can be used as the outer package. From the viewpoint of cost and cost, it is preferable to use an aluminum laminate film.
  • the configuration of the secondary battery according to the present embodiment is not particularly limited.
  • an electrode element in which a positive electrode and a negative electrode are opposed to each other and an electrolytic solution are included in an exterior body. It can be set as a structure.
  • the shape of the secondary battery is not particularly limited, and examples thereof include a cylindrical shape, a flat wound rectangular shape, a laminated rectangular shape, a coin shape, a flat wound laminated shape, and a laminated laminated shape.
  • FIG. 1 is a schematic cross-sectional view showing the structure of an electrode element included in a laminated secondary battery using a laminate film as an outer package.
  • This electrode element is formed by alternately stacking a plurality of positive electrodes c and a plurality of negative electrodes a with a separator b interposed therebetween.
  • the positive electrode current collector e of each positive electrode c is welded to and electrically connected to each other at an end portion not covered with the positive electrode active material, and a positive electrode terminal f is welded to the welded portion.
  • a negative electrode current collector d of each negative electrode a is welded and electrically connected to each other at an end portion not covered with the negative electrode active material, and a negative electrode terminal g is welded to the welded portion.
  • the electrode element having such a planar laminated structure does not have a portion with a small R (region close to the winding core of the wound structure, folded region of the flat wound structure, etc.), the electrode element having the wound structure Compared to an element, there is an advantage that it is less susceptible to an adverse effect on the volume change of the electrode accompanying charge / discharge.
  • Example 1 lithium manganese composite oxide (LiNi 0.5 Mn 1.37 Ti 0.13 O 4 , hereinafter referred to as 5V class manganese spinel) was used as the positive electrode active material.
  • Graphite particles were used as the negative electrode active material.
  • electrolytic solution having the composition shown in Table 2, a lithium ion battery cell was produced by the following procedure.
  • the obtained positive electrode was cut into a shape in which a positive electrode active material layer of 28 mm ⁇ 13 mm and a current collector of 5 mm ⁇ 5 mm extended to the left short side portion thereof.
  • the negative electrode was also cut into a shape in which a negative electrode active material layer of 30 mm ⁇ 14 mm and a current collector of 5 mm ⁇ 5 mm extended to the right short side portion thereof.
  • the cut out positive electrode and negative electrode were laminated via a separator.
  • a tab with an aluminum sealant having a width of 5 mm, a length of 20 mm, and a thickness of 0.1 mm was connected to the positive electrode current collector, and a tab with the same size nickel sealant was connected to the negative electrode current collector.
  • the tab and the current collector were integrated by ultrasonic welding.
  • a non-aqueous electrolytic solvent is prepared by mixing 50:50 (volume ratio) of tetramethylene sulfone aqueous solvent as the sulfone compound and methyl 2,2,3,3-tetrafluoropropionate as the fluorine-containing ester compound. did. LiPF 6 as a supporting salt was mixed with the nonaqueous electrolytic solvent so as to be 1 M to obtain an electrolytic solution.
  • the charge / discharge cycle characteristic in high temperature conditions was evaluated.
  • the charge / discharge conditions were a temperature of 45 ° C., a charge rate of 1.0 C, a discharge rate of 1.0 C, a charge end voltage of 4.75 V, and a discharge end voltage of 3.0 V.
  • Table 2 shows the capacity retention after the cycle.
  • Capacity maintenance ratio (%) was calculated by (discharge capacity after 50 cycles or 100 cycles) / (discharge capacity after 5 cycles) ⁇ 100 (unit:%).
  • Gas generation evaluation The amount of gas generation was evaluated by measuring the change in cell volume after the charge / discharge cycle. The cell volume was measured using the Archimedes method, and the gas generation amount was calculated by examining the difference before and after the charge / discharge cycle. Table 2 shows the amount of gas generated after each cycle.
  • the secondary battery (Example 1) using a non-aqueous electrolytic solvent containing a fluorine-containing ester compound and a sulfone compound has a higher capacity retention rate after charge and discharge than the comparative example, and the gas The amount generated was reduced to less than half.
  • Example 2 Even in the secondary battery using the nonaqueous electrolytic solvent in which a part of SL of the nonaqueous electrolytic solvent in Example 1 is replaced with PC (Example 2), the capacity retention rate after charging and discharging is compared with the comparative example. The gas generation amount was reduced to less than half.
  • a non-aqueous secondary battery comprising an electrolytic solution containing a supporting salt and a non-aqueous electrolytic solvent
  • the nonaqueous electrolytic solvent includes a sulfone compound represented by the following formula (1) and a fluorine-containing ester compound represented by the following formula (A):
  • the content of the sulfone compound is 20% by volume or more and 70% by volume or less in the nonaqueous electrolytic solvent
  • a content of the fluorine-containing ester compound is 20% by volume or more and 60% by volume or less in the non-aqueous electrolytic solvent;
  • R 1 and R 2 each independently represents a substituted or unsubstituted alkyl group.
  • the carbon atom of R 1 and the carbon atom of R 2 are bonded via a single bond or a double bond. And may form a ring structure).
  • R a and R b each independently represents an alkyl group or a fluorine-substituted alkyl group, and at least one of R a and R b is a fluorine-substituted alkyl group.
  • R 3 represents a substituted or unsubstituted alkylene group
  • m is an integer of 1 to 10).
  • R 5 is —CH 3 , —C 2 H 5 , or —C 3 H 7
  • R 6 R 7 —CH 2 —COO—R 8 (D)
  • R 8 is —CH 3 , —C 2 H 5 , or —C 3 H 7 ).

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  • General Physics & Mathematics (AREA)
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Abstract

L'objet du présent mode de réalisation consiste à proposer une batterie secondaire non aqueuse qui supprime efficacement la décomposition d'un fluide électrolytique, même dans des conditions de tension élevée et de température élevée, et qui possède des caractéristiques de cycle à long terme supérieures. La batterie secondaire non aqueuse, qui comprend un fluide électrolytique contenant un milieu électrolytique non aqueux et un électrolyte de conductivité, est caractérisée par : le milieu électrolytique non aqueux contenant un composé sulfone représenté par une formule prédéterminée et un composé ester contenant du fluor représenté par une formule prédéterminée ; la quantité du composé sulfone contenu représentant 20 à 70 % en volume, milieu électrolytique non aqueux inclus ; et la quantité de composé ester contenant du fluor contenu représentant 20 à 60 % en volume, milieu électrolytique non aqueux inclus.
PCT/JP2012/071168 2011-09-20 2012-08-22 Batterie secondaire non aqueuse Ceased WO2013042503A1 (fr)

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JPWO2015080102A1 (ja) * 2013-11-28 2017-03-16 日本電気株式会社 二次電池用電解液およびこれを用いた二次電池
JP2018106883A (ja) * 2016-12-26 2018-07-05 ダイキン工業株式会社 電解液、電気化学デバイス、リチウムイオン二次電池、及び、モジュール
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CN112470318A (zh) * 2018-07-31 2021-03-09 株式会社日本触媒 电解质组合物、电解质膜及电解质膜的制造方法

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WO2020183894A1 (fr) * 2019-03-11 2020-09-17 パナソニックＩｐマネジメント株式会社 Batterie secondaire à électrolyte non aqueux
DE102021113877A1 (de) 2021-05-28 2022-12-01 Bayerische Motoren Werke Aktiengesellschaft Lithiumionen-Batterie mit einer Elektrolytzusammensetzung und einem manganreichen Kathodenaktivmaterial sowie Verwendung der Elektrolytzusammensetzung
CN117497858B (zh) * 2023-12-13 2025-11-18 蜂巢能源科技股份有限公司 一种电解液和锂离子电池

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